Disazo dyes containing higher acylamino group



Patented May 6, 1947 v DlSA-ZO DYES. GONTAININQJHIGHER ACYL'AMINO Henry Charles OIpin, Ediii'l'iird "Stanley, and Christopher Stanley Argyle, spanatn, near Derby, England, assignor's to British Celanes'e Limited, London, England; a company of Great Britain No Drawing. Application 1e'f4 2 ,'sjer a1 N 448,834. In Great Britain July 1941 7 Claims. (01. 26.0 187) V invention relates to the manufacture of ne'W-dis'az'o dyes and other polyazo dyes and more particularly to the manufacture'of dyes of this which are soluble in organic liquids and are useful for colouring solutions of film-forming ma terials in organic liquids.

According to the present invention the new disazo and "other polyazo dyes are obtained by coupling a diaz'otise'd annno-azo compound with an N di aikyi aniline er other N 'substituted aniline capable of coupling in para position to the amino group and having, as a substituent in meta position to the substituted amino group, an aminogroup acidylat'ed with an aliphatic acid containing at least 9 carbon atoms. An N-diai kyl aniline of this character is, for instance, a ii-stearoy-l amino-l-diethyl amino benzene twhich can be obtained by the action of stea-ric and chloride on 3-a m-ino-1-tiiethyl-amino-ben- "These new dyes are very valuable for ineor por'atioh in fibres of cellulose acetate or other cellulose ester or ether, In the first place, with their aid it is possible to impart to such fibres colourationsw-hieh are very resistant to aqueous treatment and are clear and ne rrom any greasy appearance. Second-1y, they are for the most part of very good solubility in organic liquids, aramany aeeto'ne, and there'fore can be dissolved in the cellulose ester or ether solutions from which fibres are most conveniently manufactured. Coloured films, foils and similar shaped articles of cellulose acetate or other cellulose esters or ethers containing thesedyes are described and ciaimeamte aha, in companionT-J; 'S. applicatl'ori 8; No; l l 8-,833',filel il'unefih masts Pat-'- 'ent No.2-,39 3,65'2'. 1

The coupling component, namely the N-sea stituted-aniline having, as a substituent in the meta position to the amino group, an amino group acidylated with aliphatic acid containing at least 19 carbon atoms, should be one capable of coupling inpara positionto the substitutedamino group- The "Nasubstituents of a coupling component can ice, for example, alkyl, .cyelo-alkyl; aryl, eraralkyl groups, ior example methyl, ethyl, betahydroxyfethyl, or beta-.hydroxypropyl, cyclehex'yl. 'or benzyl.

Coupling components particularly suitable for purposes of the invention, are the mono=acidyl= maphenyl'ene diamines Jof the general formula I x R2 2 wherein X represents hydrogen, halogen, alkyl or alkoxy (including substituted alkoxy, e. g. beta-hydroxyethoXy), Ac represents an acidyl group derived from an aliphatic acid containing at least 9 'carbbn atoms, R1 represents hydrogen or alkyl (including substituted alkyl, e. g. beta:- hydroxy eth yl or other hydroxyalkyl), .and R2 and R3 represent organic substituents for example, 'aik yl, aryl, aralkyl or cycloalkyl groups (in.- cluding substituted alkyl, aryl, aralkyl or cycloalkyl groups) or where R2 represents an organic substituents and Ra represents hydrogen. if desired R2 and R3 may together constitute a chain of methylene groups forming, together with the associated nitrogen. atom, a heterocyclic, ring,-;f.or example. the pineridine V The acid raidicle of the acidy-lamino, group present in the coupling component is advantageously one containing at least 12 carbon atoms and may be either saturated or unsaturated. Examples of such radicles are those of lauriciaQid, palmitic acid, stearic acid and oleic acid.

Diazo components suitable for the purposes of the invention are azo-benzenes, azoalphanaphthalenes and benzen -aZ Ph i a lenes containing onev or 'two diazotisable amino groups in para positions to 210 groups. Substituents may be present in addition to the diazotisable amino groups and'the azo groups, for ex? ample alkyl groups, aciclylamino groups, alkoxy groups, e. g. methoxy or ethoxy groups, halogen atoms or nitro groups, the latter two types of substituents more particularly in a nucleus which does not contain a diazotisableamino group. Acidylamino groups, when present, can be those in which the acidyl radicle is that of an aromatic or aliphatic carboxylic acid, for example of bene zoic acid, or of acetic acid, or other iatty acid containing less than 5 carbon atoms. Sulphonic and carboxylic groups are preferably absent from the diazo components.

Amino-ago compounds, very useful as diazo components, are those obtainable by coupling with para-coupling primary amines diazo compounds of anilineytoluidines, 'anisidines, phenetidi-nes, alpha-naphthylamine, and their halogen, nitro, and-halogen-nitro derivatives (e. g. 6-, 'm-, andp-r i-troaniline, z-cmor- -nitmannme, and fl-chloriienitraniline) V Thepara-coupling .pri-'- mary amines include such as contain acidylamino groups; those containing an acidylamino group inrmeta position to the primary amino group and especially those containing in addition an alkoxy group parato the acidylamino group are particularly useful. Specific para-coupling primary amines are m-to11ndine-, cresidine, p-xylicline,

' 2'z5 'dimethoxy aniline, 2:5 diethoxy aniline,

amine and 1-amino-3-acetyl-methylamino ben- Of particular value as diazo components for the purpose of the invention are 4-nitro-4- amino-azo-benzenes, for example 4-nitro-4- aminoazo-benzene itself or its substitution products in which the substituents are, forexample, alkyl, halogen, alkoxy, or acidylamino. 4-nitro-4-amino-azo-benzenes having in the benzene nucleus containing the amino group two of these substituents in para position one tothe other, are of especial interest both by reason of their ready availability and by reason of their yielding, in conjunction with the coupling com- .ponents employed according to the invention, shades which, as compared with those obtained in the absence of the two substituents, are displaced towards the blue end of the colour series extending from yellow to green through orange, red and blue.

Diamino azo compounds can also be used, e. g. those which can be obtained by reducing a nitro group of such of the above mono-amino azo com pounds as contain a nitro group. V

The following are specific examples of aminoazo compounds which'can be used:

4-nitro-l-amino-2' :5-dimethoxy-azo-benzene 4-nitro-4"-amino-2' :5'-diethoxy-azo-benzene 4-nitrobenzene-azo-alpha-naphthylamine 4-nitro-2-chlorbenzene-azo alpha naphthyl amine 4-nitro-2-chlor-4-amino-2-methyl-5-methoxyazo-benzene 4-nitro-4'-amino-2'-acetylamino -'5 methoxy Lamina- 1-sulpho-azo-benzene As coupling components for the production of the new dyes especial mention may be made of the mono-acidyl-m-phenylene diamines of the formula given above, wherein X is hydrogen, and particularly those compounds where B and R1 are hydrogen, R2 and R3 are alkyl groups, and Ac is an acidyl group derived from a fatty acid containing at least 9 carbon atoms. Examples of such compounds are the 3-stearoyl-amino and B-Iauroylamino derivatives of N-diethyl-aniline, N -dimethyl-aniline and N di(beta hydroxyethyl) -aniline. Coupling components of the 'above general formula in which X is-a substituent,

Those 7.1

amino-benzene and 3-amino-G-methyl-l-diethylamino benzene.

The 3 -stgaroylaminogli-diethyleaniline gives violet to blue dyes with the diazo compounds of the above list of specific amino-azo compounds with the exception of those of the last two compounds with which it yields red products.

The coupling of the diazotised amino-azo compound with the coupling component is advantageously affected in a medium consisting to a. substantial extent, e. g. 50% or more, of a watersolubleorganic liquid; for example acetic acid or methyl, ethyl, or propyl alcohol. Thus diazotisation can be effected in acetic acid medium and acetic acid diazo solution run into a. solution of the coupling component in ethyl alcohol." Again an aqueous diazo solution can be prepared and run into an ethyl alcohol solution of the coupling component. The coupling medium should be acid during the coupling operation.

The invention is illustrated by the following examples:

Example I 138 parts of p-nitraniline are diazotised in the usual manner in aqueous solution by means of hydrochloric acid and sodium nitrite and the solution added with good stirring to a solution of 153 parts of 2:5-dimethoxyaniline and 120 parts of hydrochloric acid (32 Tw.) in 10,000 parts of water. After stirring for 1 hour the liquid is made neutral to Congo Red paper and the monoazo product is filtered oh and dried. 302 parts of finely ground product are suspended in 1800 parts of acetic acid and added slowly to a solution of nitrosyl sulphuric acid prepared by dissolving 69 parts of sodium nitrite in 1300 parts of sulphuric acid, warming to 70 C., and cooling for example alkoxy, can also be used.' Such coupling components are the N-stearoyl deriva tives of the 3-a min o-6-methoxy-l di'ethylto 10 C. The temperature is maintained. at 10-15 C. during the addition and for 1 /2 hours after the base has been added. Alter filtering, the solution of the diazotised base is added gradually to a cooled solution of 430 parts of mstearoylamino-diethylaniline in 5000 parts of methylated spirits and sodium acetate is added to neutralise the sulphuric acid. After stirring for 2 hours water is added till the dyestufi is precipitated. The dyestufi is now filtered, washed with methylated spirits and with water, dried, and finely ground.

It gives a navy blue solution in acetone, and is readily soluble in a 25%, solution of cellulose acetate in acetone. This latter solution can be spun into filaments of blue shade which are very resistant to aqueous treatment.

Example II 198 parts of aminoazobenzene and 340 parts of hydrochloric acid (32 Tw.) are ground to a paste and dilutedwith 1000 parts of water and 1000 parts of ice. The base is then diazotised by addition of 70 parts of sodium nitrite dissolved in a little water. After filtering ofi any insoluble matter, the solution of the diazotised base is added to a solution of 430 parts of m-stearoylaminodiethylaniline in 3000 parts of methylated spirits. The mixture is stirred for 2 hours and sodium acetate is added to complete the coupling. The dyestuif is then filtered off, washed, dried and finely ground, It gives bluish-red shades in acetone and is readily soluble in a 25% solution of cellulose acetate in acetone. The coloured cellulose acetate solutions can be spun into filaments of red shade very resistant to aqueous treatment.

Having described our invention what we desire to secure by Letters Patent is:

1. A disazo dye of the formula AN=NY where A is an azo benzene residue and Y is the residue of an N-alkyl aniline having as a substituent in meta position to the N-alkylamino group an amino group acidylated with an aliphatic monocarboxylic acid containing from 16 to 18 carbon atoms, said residue Y being united to the azo group at the para position to the alkylamino group.

2. A disazo dye of the formula AN=N--Y where A is an azo benzene residue attached to the azo group at the 4'-position and having a nitro group in the 4-position, and Y is the residue of an N-alkyl aniline having as a substituent in meta position to the N-alkylamino group an amino group acidylated with an aliphatic monocarboxylic acid containing from 16 to 18 carbon atoms, said residue Y being united to the azo group at the para position to the alkylamino group.

3. A disazo dye of the formula where A is an azo benzene residue. 4. A disazo dye of the formula NHstearoyi where A is an azo benzene residue attached to the azo group at the 4'-position and having a nitro group in the 4-position.

5. A disazo dye of the formula OCIJHs l l 0 CH3 N Hstearoyl 6. Process for the production of an azo dye, which comprises coupling a diazotized aminoazo compound of which the aryl nuclei are selected from the nuclei of the benzene series and nuclei of the naphthalene series with an N-alkyl aniline capable of coupling in para position to the N-alkylamino group and having as a substituent in meta position to the N-alkyl-amino group an amino group acidylated with an aliphatic mono-carboxylic acid containing from 16 to 18 carbon atoms.

'7. Process for the production of an azo dye which comprises coupling a diazotized 4-nitro- 4'-amino-azobenzene with 3-stearoylamino-N- diethylaniline.

HENRY CHARLES OLPIN. EDMUND STANLEY, CHRISTOPHER STANLEY ARGYLE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,111,300 Senn Mar. 15, 1938 2,289,413 Ellis et a1 July 14, 1942 2,083,308 Senn June 8, 1937 

